JP7621769B2 - toner - Google Patents

Description

This disclosure relates to toners used in recording methods that utilize electrophotography, electrostatic recording, and toner jet recording methods.

Methods of visualizing image information via an electrostatic latent image, such as electrophotography, are applied to copying machines, multifunction machines, and printers, and in recent years, there has been a demand for further cost reduction and higher image quality.
In this situation, toner is required to reproduce the latent image faithfully. In order to reproduce the latent image faithfully, it is effective to precisely control the charge of the toner. If the charge control of the toner is insufficient, problems such as fogging, in which low-charged toner is developed in non-image areas, and regulation failure, in which over-charged toner is fused to the toner carrier, occur, which are factors that hinder the faithful reproduction of the latent image.
Conventionally, as a toner charging process, frictional charging, in which a charge is imparted to a toner by rubbing between the toner and a carrier or a charging member (hereinafter collectively referred to as a charging member), has been widely studied.
However, in triboelectric charging, the friction between the charging member and the toner does not occur uniformly, and overcharged toner and undercharged toner may occur because the charge due to triboelectric charging occurs only at the portion where the toner and the charging member come into contact.
In addition, triboelectric charging is easily affected by humidity, and the amount of charge may change between low and high humidity environments. Furthermore, triboelectric charging is greatly affected by the fluidity of the toner, and therefore the amount of charge may change if the toner deteriorates due to long-term use and the like, causing a decrease in fluidity.

In order to solve these problems in the friction charging process, an injection charging process has been investigated. In the injection charging process, the toner is charged by injecting electric charge due to a potential difference between the toner and a charging member.
In this case, if a conductive path exists within or between the toner particles, the entire toner particle can be uniformly charged, not just the portion in contact with the charging member.
In addition, with injection charging, the charge amount can be controlled as desired by changing the potential difference, making it easier to meet the charge amount required by the system. Furthermore, since injection charging is not easily affected by humidity, it is possible to suppress changes in the charge amount due to the environment.
However, the injection charging process has the problem that it is difficult to simultaneously inject and retain charge, because the presence of conductive paths within or between toner particles makes it easy for the injected charge to leak, resulting in a trade-off between charge injection and charge retention.

Patent Literature 1 discloses a toner whose volume resistivity decreases under high voltage and an injection charging process using the toner. The process described in Patent Literature 1 aims to eliminate the trade-off between charge injection properties and charge retention properties by performing only the charge injection process into the toner under high voltage at which the volume resistivity of the toner decreases.
From another perspective, Japanese Patent Application Laid-Open No. 2003-233663 discloses a toner in which the surfaces of the toner base particles are coated with metal fine particles and an organosilicon compound, with the aim of achieving both control of charging characteristics and durability.

JP 2005-148409 A JP2019-133145Publication

In Patent Document 1, in order to achieve injection charging in the above process, a high voltage is required in the charge injection process, which makes it easy for discharge to occur and makes it difficult to precisely control the amount of charge. In addition, other processes must be achieved at low voltages, which limits the design freedom in voltage setting of the processes.
The toner described in Patent Document 2 has excellent charge build-up properties in a conventional friction charging process, and at the same time, is less likely to cause contamination of components and has excellent durability.
On the other hand, because there is a lack of means for injecting charge into the toner base particles, charge tends to be retained on the surface of the toner particles, and as a result, charge tends to leak through the metal fine particles on the surface of the toner particles, resulting in insufficient charge retention, and so improvements are needed to apply this to the injection charging process.
As described above, a toner that satisfies both high charge injection properties and high charge retention properties in the injection charging process has not yet been obtained, and further improvement is required.
The present disclosure provides a toner that enables precise charge control and achieves high image quality by achieving both charge injection properties and charge retention properties in the injection charging process.

The present disclosure relates to a toner having toner particles containing a binder resin,
the toner particles contain a condensation product of an organosilicon compound,
In a time-of-flight secondary ion mass spectrometry (TOF-SIMS) of the toner particles,
the normalized intensity of a silicon ion (m/z 28) represented by the following formula (I) derived from a condensation product of the organosilicon compound is 7.00×10 ⁻⁴ or more and 3.00×10 ⁻² or less;
Normalized silicon ion intensity (m/z28)={ion intensity of silicon ion (m/z28)}
/ {total ion intensity at m / z 0.5 to 1850} ... (I)
the normalized intensity of silicon ions (m/z 28) measured by time-of-flight secondary ion mass spectrometry after sputtering the toner particles with an Ar gas cluster ion beam (Ar-GCIB) under the following condition (A) is 6.99×10 ⁻⁴ or less;
(A) Acceleration voltage: 5 kV, current: 6.5 nA, raster size: 600 x 600 μm, irradiation time: 5 sec/cycle, sputtering time: 250 sec
The toner has fine particles on the surface of the toner particles,
The toner relates to a toner in which the fine particles have at least one selected from the group consisting of polyvalent acid metal salt fine particles which are a reaction product of a compound containing at least one of Ti and Al elements with a polyvalent acid, strontium titanate fine particles, titanium oxide fine particles, and aluminum oxide fine particles.

According to the present disclosure, a toner is provided that achieves both charge injection properties and charge retention properties in the injection charging process, enabling precise charge control and achieving high image quality.

In this disclosure, the expressions "XX or more and YY or less" and "XX to YY" representing a numerical range mean a numerical range including the endpoints, that is, the lower limit and the upper limit, unless otherwise specified.
When numerical ranges are stated in stages, the upper and lower limits of each numerical range can be combined in any way.

For a toner to have a high degree of injection charging suitability, it is important that the toner has a property in which charge transfer occurs only in the charge injection process and does not occur in other processes. The present inventors considered that, in order for a toner to have the above-mentioned properties, a configuration is required in which charge can be injected not only near the toner surface but also into the toner interior in the injection charging process, and charge leakage from the toner surface is unlikely to occur in processes other than the injection charging process.
As a result of extensive research, the present inventors have found that a toner having the following composition can achieve both charge injection and charge retention in the injection charging process.

That is, the present disclosure provides a toner having toner particles containing a binder resin,
the toner particles contain a condensation product of an organosilicon compound,
In a time-of-flight secondary ion mass spectrometry (TOF-SIMS) of the toner particles,
the normalized intensity of a silicon ion (m/z 28) represented by the following formula (I) derived from a condensation product of the organosilicon compound is 7.00×10 ⁻⁴ or more and 3.00×10 ⁻² or less;
Normalized silicon ion intensity (m/z28)={ion intensity of silicon ion (m/z28)}
/ {total ion intensity at m / z 0.5 to 1850} ... (I)
the normalized intensity of silicon ions (m/z 28) measured by time-of-flight secondary ion mass spectrometry after sputtering the toner particles with an Ar gas cluster ion beam (Ar-GCIB) under the following condition (A) is 6.99×10 ⁻⁴ or less;
(A) Acceleration voltage: 5 kV, current: 6.5 nA, raster size: 600 x 600 μm, irradiation time: 5 sec/cycle, sputtering time: 250 sec
The toner has fine particles on the surface of the toner particles,
The toner relates to a toner in which the fine particles have at least one selected from the group consisting of polyvalent acid metal salt fine particles which are a reaction product of a compound containing at least one of Ti and Al elements with a polyvalent acid, strontium titanate fine particles, titanium oxide fine particles, and aluminum oxide fine particles.

The present inventors consider this mechanism as follows.
In the above toner configuration, when charge is injected in the injection charging process, it is believed that the metal-containing fine particles with excellent conductivity present on the toner quickly receive a large amount of charge, and then the charge is transferred to the condensation product of an organosilicon compound having a silyl group, which is easily negatively charged, on the surface of the toner particle.
In this case, in a process where a large amount of charge is intentionally applied, such as injection charging, the metal-containing fine particles become overcharged, which is thought to facilitate the transfer of charge to the condensation products of the organosilicon compounds in the vicinity of the metal-containing fine particles that are not in contact with the metal-containing fine particles, and a charging effect can be expected even with a small amount of the condensation products of the organosilicon compounds.
Furthermore, the condensation product of the organosilicon compound interacts with the binder resin, promoting the transfer of charge within the toner. This series of steps allows charge to be uniformly and quickly injected from the metal-containing fine particles into the toner via the small amount of the condensation product of the organosilicon compound present near the surface of the toner particles, resulting in high charge injection properties.

On the other hand, after passing through the injection charging process, it is believed that the highly conductive metal-containing fine particles become the starting point for leaking charge. At this time, by limiting the amount of condensation products of organosilicon compounds, which easily mediate the transfer of charge, to an extremely small amount near the surface of the toner particles, it is possible to minimize the transfer of charge from the inside of the toner to the toner surface and the transfer of charge due to contact between the condensation products of organosilicon compounds and metal-containing fine particles.
That is, the leakage of electric charge from inside the toner is suppressed, and high charge retention can be achieved.

Taking the above mechanism into consideration, the toner will be described.
Examples of the condensation product of an organosilicon compound include condensation products of organosilicon compounds such as silane coupling agents, silane-modified resins reacted with silane coupling agents or hydrosilanes, polymers of organosilicon compounds, hybrid resins thereof, and condensation products of these in combination. Condensation products of silane coupling agents and silane-modified resins R having a structure represented by the following formula (1) are preferred.
As the silane coupling agent, known organosilicon compounds can be used without any particular limitation. Specific examples include the following bifunctional silane compounds having two functional groups and trifunctional silane compounds having three functional groups.
Examples of bifunctional silane compounds include dimethyldimethoxysilane and dimethyldiethoxysilane.

Examples of trifunctional silane compounds include the following.
trifunctional silane compounds having an alkyl group as a substituent, such as methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, and decyltriethoxysilane;
Trifunctional silane compounds having an alkenyl group as a substituent, such as vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, and allyltriethoxysilane;
Trifunctional silane compounds having an aryl group as a substituent, such as phenyltrimethoxysilane and phenyltriethoxysilane;
Trifunctional silane compounds having a methacryloxyalkyl group as a substituent, such as γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxyoctyltrimethoxysilane, γ-methacryloxypropyldiethoxymethoxysilane, γ-methacryloxypropylethoxydimethoxysilane, and 3-methacryloxypropyltris(trimethylsiloxy)silane;
Trifunctional silane compounds having an acryloxyalkyl group as a substituent, such as γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxyoctyltrimethoxysilane, γ-acryloxypropyldiethoxymethoxysilane, and γ-acryloxypropylethoxydimethoxysilane.

It is more preferable that the condensation product of the organosilicon compound is a silane-modified resin R having a structure represented by the following formula (1). When the toner particles have silane-modified resin R as the condensation product of the organosilicon compound, the efficiency of charge propagation into the toner particles is improved, and the charge amount is further improved.

(In the formula (1), ^P1 represents a polymer moiety, ^L1 represents a single bond or a divalent linking group, ^R1 to ^R3 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 or more carbon atoms, an alkoxy group having 1 or more carbon atoms, an aryl group having 6 or more carbon atoms or a hydroxy group, m represents a positive integer, and when m is 2 or more, a plurality of L1 ^'s , a plurality of R1 ^'s , a plurality of R2 ^'s and a plurality of R3 ^'s may be the same or different, with the proviso that Si is bonded to at least one carbon, and at least one of ^R1 to ^R3 is condensed with an organosilicon compound.)

When at least one of R ¹ to R ³ is condensed with an organosilicon compound, the group condensed with the organosilicon compound has an —O—Si≡ structure.
At least one of R ¹ to R ³ in the formula (1) preferably represents an alkoxy group having 1 or more carbon atoms, or a hydroxy group. More preferably, the groups among R ¹ to R ³ that are not condensed with the organosilicon compound each independently represent an alkoxy group having 1 or more carbon atoms, or a hydroxy group.
Of the above substituents, the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 4. The number of carbon atoms in the alkoxy group is preferably 1 to 20, more preferably 1 to 4, even more preferably 1 to 3, and particularly preferably 1 or 2. The number of carbon atoms in the aryl group is preferably 6 to 14, more preferably 6 to 10.

The content of silicon atoms in the resin R is preferably 0.02% by mass to 10.00% by mass, more preferably 0.10% by mass to 5.00% by mass, and further preferably 0.50% by mass to 2.00% by mass.
The content of resin R relative to 100.0 parts by mass of binder resin is preferably 0.10 parts by mass to 10.00 parts by mass, more preferably 0.20 parts by mass to 5.0 parts by mass, and even more preferably 0.50 parts by mass to 2.0 parts by mass.

^P1 in the formula (1) is not particularly limited, and examples thereof include a polyester resin moiety, a vinyl resin moiety, a styrene acrylic resin moiety, a polyurethane resin moiety, a polycarbonate resin moiety, a phenol resin moiety, and a polyolefin resin moiety.
Among these, it is preferable that ^P1 contains a styrene acrylic resin moiety or a polyester resin moiety. For example, ^P1 may be a hybrid resin moiety of a polyester resin and a styrene acrylic resin. It is more preferable that ^P1 has a polyester resin moiety. When ^P1 is a polyester resin moiety, the interaction with the binder resin is high, the injection chargeability is further improved, and a high charge amount can be obtained even at a low voltage.

When the weight average molecular weight of the silane-modified resin R having the formula (1) structure is MwA, MwA is preferably 8000 or more and 50000 or less. When MwA is 8000 or more, the amount of low molecular weight components is reduced, and heat-resistant storage stability is likely to be improved. When MwA is 50000 or less, the molecular mobility is high after fixing, and spatial arrangement is easily achieved, and thus discharge adhesiveness is likely to be improved.
More preferably, MwA is from 12000 to 30000. MwA can be controlled by changing the reaction temperature, reaction time, monomer composition, amount of initiator, etc. of the resin.

Any method may be used to form the silane-modified resin R having the structure of formula (1), and examples thereof include the following methods.
The resin can be formed by reacting a carboxyl group in a resin with an aminosilane coupling agent, by polymerizing an ethylenically unsaturated bond site or a monomer having an ethylenically unsaturated bond in a resin with a (meth)acrylic silane coupling agent, by reacting a hydroxyl group in a resin with an isocyanate silane coupling agent, or by reacting an isocyanate group in a resin with an aminosilane coupling agent.

Examples of the aminosilane coupling agent include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, and 3-aminopropylmethoxydimethylsilane.
Examples of the (meth)acrylic silane coupling agent include 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltriethoxysilane, 8-acryloxyoctyltriethoxysilane, 8-methacryloxyoctyltriethoxysilane, 3-[acrylate (triethoxysilyl)methyl, 3-methacrylate (triethoxysilyl)methyl, 3-[dimethoxy(methyl)silyl]propyl, 3-[dimethoxy(methyl)silyl]propyl, acrylate [dimethoxy(methyl)silyl]methyl, methacrylate [dimethoxy(methyl)silyl]methyl, 3-(methacryloyloxy)propyltris(trimethylsilyloxy)silane, and the like.
Examples of the isocyanate coupling agent include isocyanatomethyltrimethoxysilane, isocyanatomethyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-isocyanatopropylmethyldimethoxysilane.

When the ^P1 structure of the silane-modified resin R having the structure of formula (1) is a polyester resin moiety, examples of the condensation polymerization monomer that can be used to produce the polyester resin moiety include polyvalent carboxylic acids and polyhydric alcohols.
Examples of polyvalent carboxylic acids include oxalic acid, glutaric acid, succinic acid, maleic acid, adipic acid, β-methyladipic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, fumaric acid, citraconic acid, diglycolic acid, cyclohexane-3,5-diene-1,2-dicarboxylic acid, hexahydroterephthalic acid, malonic acid, pimelic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, p-phenylene diacetic acid, m-phenylenediglycolic acid, p-phenylenediglycolic acid, o-phenylenediglycolic acid, diphenylacetic acid, diphenyl-p,p'-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracene dicarboxylic acid, and cyclohexane dicarboxylic acid.
Examples of polycarboxylic acids other than dicarboxylic acids include trimellitic acid, pyromellitic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, pyrene tricarboxylic acid, and pyrene tetracarboxylic acid.

Polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, and dipentaerythritol. , tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, isosorbide, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, hydrogenated bisphenol A, hydrogenated bisphenol A ethylene oxide adduct, hydrogenated bisphenol A propylene oxide adduct, etc.

The polyester resin is not particularly limited, but is preferably a condensate of a dialcohol and a dicarboxylic acid. For example, a polyester resin having a structure represented by the following formula (6) and at least one structure (multiple structures can be selected) selected from the group consisting of structures represented by the following formulas (7) to (9) is preferred. Alternatively, a polyester resin having a structure represented by the following formula (10) is also preferred.

(In formula (6), R ⁹ represents an alkylene group, an alkenylene group, or an arylene group. In formula (7), R ¹⁰ represents an alkylene group or a phenylene group. In formula (8), R ¹⁸ represents an ethylene group or a propylene group. x and y each represent an integer of 0 or more, and the average value of x+y is 2 to 10. In formula (10), R ¹¹ represents an alkylene group or an alkenylene group.)

Examples of the alkylene group (preferably having 1 to 12 carbon atoms) for R ⁹ in the above formula (6) include the following: methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, hexamethylene group, neopentylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, 1,3-cyclopentylene, 1,3-cyclohexylene, and 1,4-cyclohexylene group.
Examples of the alkenylene group (preferably having 2 to 4 carbon atoms) for R ⁹ in the above formula (6) include a vinylene group, a propenylene group, and a 2-butenylene group.
Examples of the arylene group (preferably having 6 to 12 carbon atoms) for R ⁹ in the above formula (6) include a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, a 2,6-naphthylene group, a 2,7-naphthylene group, and a 4,4'-biphenylene group.
^R9 in the above formula (6) may be substituted with a substituent. In this case, examples of the substituent include a methyl group, a halogen atom, a carboxy group, a trifluoromethyl group, and combinations thereof.

Examples of the alkylene group (preferably having 1 to 12 carbon atoms) for R ¹⁰ in the above formula (7) include the following: methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, hexamethylene group, neopentylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, 1,3-cyclopentylene, 1,3-cyclohexylene, and 1,4-cyclohexylene group.
Examples of the phenylene group for R ¹⁰ in the above formula (7) include a 1,4-phenylene group, a 1,3-phenylene group, and a 1,2-phenylene group.
R ¹⁰ in the above formula (7) may be substituted with a substituent. In this case, examples of the substituent include a methyl group, an alkoxy group, a hydroxy group, a halogen atom, and combinations thereof.

Examples of the alkylene group (preferably having 1 to 12 carbon atoms) for R ¹¹ in the above formula (10) include the following: methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, hexamethylene group, neopentylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, and 1,4-cyclohexylene group.
Examples of the alkenylene group (preferably having 2 to 40 carbon atoms) in R ¹¹ in the above formula (10) include the following: vinylene group, propenylene group, butenylene group, butadienylene group, pentenylene group, hexenylene group, hexadienylene group, heptenylene group, octanylene group, decenylene group, octadecenylene group, eicosenylene group, and triacontenylene group. These alkenylene groups may have any of a linear, branched, and cyclic structure. The position of the double bond may be any position, as long as there is at least one double bond.
R ¹¹ in the above formula (10) may be substituted with a substituent. In this case, the substituent that may be substituted includes an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom, and combinations thereof.

When the ^P1 structure is a styrene-acrylic resin or a vinyl resin, the monomer is not particularly limited and known monomers can be used. For example, the following monomers can be used.
Styrene derivatives such as styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p-methoxystyrene, and p-phenylstyrene;
Acrylic polymerizable monomers such as methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-hydroxyethyl acrylate, and 2-benzoyloxyethyl acrylate;
Methacrylic polymerizable monomers such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, diethyl phosphate ethyl methacrylate, 2-hydroxyethyl methacrylate, and dibutyl phosphate ethyl methacrylate.

The divalent linking group that can be represented by L ¹ in the formula (1) is not particularly limited, but examples include structures represented by the following formulas (2) to (5). In these cases, the injection chargeability is further improved, and a high charge amount can be obtained even at a low voltage. This is thought to be because the interaction with the binder resin is high, and the transfer of charge to the P ¹ site is more smoothly carried out.
In the linking group, the atom bonding to Si in formula (1) is preferably a carbon atom.

In formula (2), ^R5 represents a single bond, an alkylene group or an arylene group. (*) represents a bonding site to ^P1 in formula (1), and (**) represents a bonding site to the silicon atom in formula (1).
In formula (3), ^R6 represents a single bond, an alkylene group, or an arylene group. (*) represents a bonding site to ^P1 in formula (1), and (**) represents a bonding site to the silicon atom in formula (1).
^R7 and ^R8 in formulas (4) and (5) each independently represent an alkylene group, an arylene group, or an oxyalkylene group. (*) represents a bonding site to ^P1 in formula (1), and (**) represents a bonding site to the silicon atom in formula (1).

Among these, L ¹ is preferably a divalent linking group containing an amide bond, as represented by the above formula (2).
The structure represented by the formula (2) is a divalent linking group containing an amide bond.
The linking group can be formed, for example, by reaction of a carboxy group in the resin with an aminosilane.
The aminosilane is not particularly limited, but examples thereof include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane, N-phenylγ-aminopropyltriethoxysilane, N-phenylγ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltriethoxysilane, N-6-(aminohexyl)3-aminopropyltrimethoxysilane, 3-aminopropyltrimethylsilane, and 3-aminopropylsilicon.
The alkylene group (preferably having 1 to 12 carbon atoms, more preferably 2 to 4 carbon atoms) in R ⁵ is not particularly limited, and may be, for example, an alkylene group containing an --NH-- group.
The arylene group (preferably having 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms) in R ⁵ is not particularly limited, and may be, for example, an arylene group containing a hetero atom.

The structure represented by the formula (3) is a divalent linking group containing a urethane bond.
The linking group can be formed, for example, by reaction of a hydroxy group in the resin with an isocyanate silane.
The isocyanate silane is not particularly limited, but examples thereof include 3-isocyanate propyl trimethoxy silane, 3-isocyanate propyl methyl dimethoxy silane, 3-isocyanate propyl dimethyl methoxy silane, 3-isocyanate propyl triethoxy silane, 3-isocyanate propyl methyl diethoxy silane, and 3-isocyanate propyl dimethyl ethoxy silane.
The alkylene group (preferably having 1 to 12 carbon atoms, more preferably 2 to 4 carbon atoms) in R ⁶ is not particularly limited, and may be, for example, an alkylene group containing an --NH-- group.
The arylene group (preferably having 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms) in R ⁶ is not particularly limited, and may be, for example, an arylene group containing a hetero atom.

The structure represented by the formula (4) or (5) is a divalent linking group containing a bond grafted to an ester bond in the resin.
The linking group is formed, for example, by an insertion reaction of an epoxysilane.
The insertion reaction of epoxysilane refers to a reaction including a process of inserting an epoxy group of epoxysilane into an ester bond contained in a main chain of a resin. The insertion reaction referred to here refers to, for example, a reaction described as "insertion reaction of an epoxy compound into an ester bond in a polymer chain" in Organic Synthesis Chemistry, Vol. 49, No. 3, p. 218, 1991.
The reaction mechanism of the epoxysilane insertion reaction can be represented by the following model diagram.

(In the figure, D and E represent the constituent parts of the resin, and F represents the constituent part of the epoxy compound.)
In the figure, the ring-opening of the epoxy group can involve α-cleavage or β-cleavage, resulting in two types of compounds. In either case, the epoxy group is inserted into the ester bond in the resin, in other words, the components of the epoxy compound other than the epoxy site are grafted to the resin.
The epoxy silane is not particularly limited, but examples thereof include β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and the like.

The alkylene group (preferably having 1 to 12 carbon atoms, more preferably 2 to 4 carbon atoms) in R ⁷ and R ⁸ is not particularly limited, and may be, for example, an alkylene group containing an --NH-- group.
The arylene group (preferably having 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms) in R ⁷ and R ⁸ is not particularly limited, and may be, for example, an arylene group containing a hetero atom.
The oxyalkylene group (preferably having 1 to 12 carbon atoms, more preferably 2 to 4 carbon atoms) in R ⁷ and R ⁸ is not particularly limited, and may be, for example, an oxyalkylene group containing an --NH-- group.

In addition, in a time-of-flight secondary ion mass spectrometry (TOF-SIMS) of the toner particles,
The normalized intensity of the silicon ion (m/z 28) represented by the following formula (I) derived from the condensation product of an organosilicon compound must be 7.00×10 ⁻⁴ or more and 3.00×10 ⁻² or less.
Normalized silicon ion intensity (m/z 28)={ion intensity of silicon ion (m/z 28)}/{total ion intensity at m/z 0.5 to 1850} (I)
When the normalized intensity of silicon ions (m/z28) is lower than 7.00×10 ⁻⁴ , charge injection properties are not exhibited and uniform charging performance is not obtained. When the normalized intensity of silicon ions (m/z28) is higher than 3.00×10 ⁻² , charge retention properties are not exhibited, making it difficult to achieve both charge injection properties and charge retention properties.
For higher charge retention, the normalized intensity of silicon ions (m/z 28) is more preferably 7.00×10 ⁻⁴ or more and 8.00×10 ⁻³ or less, and further preferably 8.00×10 ⁻⁴ or more and 8.00×10 ⁻³ or less.
The normalized strength in the above range indicates that the amount of silicon ions on the toner particle surface is extremely small compared to the conventional technology. It is believed that the normalized strength in the above range can be obtained by using an extremely small amount of organosilicon compound compared to the conventional technology, controlling the hydrolysis of the organosilicon compound, shortening the condensation time, and the like, thereby achieving both charge injection properties and charge retention properties.

In addition, after the toner particles are sputtered by an Ar gas cluster ion beam Ar-GCIB under the following condition (A), the normalized intensity of silicon ions (m/z 28) determined by time-of-flight secondary ion mass spectrometry must be 6.99×10 ⁻⁴ or less.
(A) Acceleration voltage: 5 kV, current: 6.5 nA, raster size: 600 x 600 μm, irradiation time: 5 sec/cycle, sputtering time: 250 sec
By performing sputtering under the condition (A), it is possible to evaluate silicon ions originating from the condensation products of the organosilicon compounds present inside the toner particles, and the fewer the condensation products of the organosilicon compounds present inside the toner particles, the more improved the charge retention. The normalized intensity is preferably 6.00×10 ⁻⁴ or less. On the other hand, the lower limit is not particularly limited, but is preferably 1.00×10 ⁻⁴ or more, and more preferably 2.00×10 ⁻⁴ or more.

Any method may be used to obtain toner particles having a desired silicon ion (m/z 28) normalized intensity. For example, when a silane-modified resin R is used as the condensation product of an organosilicon compound, a method of adding the resin R in a process of dissolving or dispersing a polymerizable monomer capable of forming a binder resin can be used.
When a condensation product of a silane coupling agent is used as the condensation product of an organosilicon compound, a method of adding a suitable amount of a silane coupling agent in a step of dissolving or dispersing a polymerizable monomer or in a step of polymerizing a polymerizable monomer to obtain toner particles and then carrying out condensation polymerization can be mentioned. Also, a method of adding a silane coupling agent to a dispersion of toner particles and carrying out condensation polymerization can be mentioned.
Since an optimal pH for the condensation polymerization reaction may exist for an organosilicon compound, the reaction can be effectively carried out by condensing the organosilicon compound at an optimal pH for the condensation polymerization reaction.

As a method for adding an organosilicon compound such as a silane coupling agent, the organosilicon compound may be added as it is, or may be mixed with an aqueous medium in advance and hydrolyzed before being added.
Examples of methods for controlling the normalized intensity of silicon ions (m/z 28) near the surface of a toner particle or inside the toner particle include methods for controlling the amount of an organosilicon compound added to form a condensation product of the organosilicon compound, the polymerization conversion rate of a polymerizable monomer, the hydrolysis time after addition of the organosilicon compound, or the condensation polymerization time.

The toner also has fine particles on the surface of the toner particles. The fine particles are at least one selected from the group consisting of polyvalent acid metal salt fine particles, which are a reaction product of a compound containing at least one of Ti and Al elements with a polyvalent acid, strontium titanate fine particles, titanium oxide fine particles, and aluminum oxide fine particles.

Among them, in order to improve the injection chargeability of the toner as a whole and obtain a more uniform charging performance, polyvalent acid metal salt fine particles which are a reaction product of a compound containing at least one of Ti element and Al element and a polyvalent acid are preferred, and it is more preferred that the metal element is Ti element.Furthermore, it is even more preferred that the polyvalent acid of the polyvalent acid metal salt fine particles is phosphoric acid, since the charge amount distribution becomes more uniform.
The content of the fine particles is preferably from 0.01 to 5.00 parts by mass, more preferably from 0.02 to 3.00 parts by mass, and even more preferably from 0.10 to 0.30 parts by mass, based on 100 parts by mass of the toner particles.

The polyvalent acid is not particularly limited and any known polyvalent acid can be used.
Among them, it is preferable that the polyacid contains an inorganic acid. Since an inorganic acid has a more rigid molecular skeleton than an organic acid, the change in properties during long-term storage is small. Therefore, it is possible to obtain stable injection charging properties even after long-term storage.
Specific examples of the polyvalent acid include inorganic acids such as phosphoric acid (trivalent), carbonic acid (divalent), and sulfuric acid (divalent); and organic acids such as dicarboxylic acids (divalent) and tricarboxylic acids (trivalent).
Specific examples of organic acids include dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, and terephthalic acid; and tricarboxylic acids such as citric acid, aconitic acid, and trimellitic anhydride.
Among these, at least one selected from the group consisting of inorganic acids phosphoric acid, carbonic acid, and sulfuric acid is preferred, and phosphoric acid is more preferred.

Specific examples of polyvalent acid metal salts include metal phosphates such as titanium phosphate compounds and aluminum phosphate compounds; metal sulfates such as titanium sulfate compounds and aluminum sulfate compounds; metal carbonates such as titanium carbonate compounds and aluminum carbonate compounds; and metal oxalates such as titanium oxalate compounds. Among these, titanium phosphate compounds are preferred.

The method for obtaining the polyvalent acid metal salt fine particles is not particularly limited, and any known method can be used. Among them, a method for obtaining the polyvalent acid metal salt fine particles by reacting a metal compound serving as a metal source with a polyvalent acid ion in an aqueous medium is preferred.
When obtaining polyvalent acid metal salt fine particles by the above-mentioned method, any conventionally known metal compound can be used as the metal source without particular limitation, so long as it is a metal compound that gives a polyvalent acid metal salt upon reaction with a polyvalent acid ion.

Specific examples of the metal chelates include titanium lactate, titanium tetraacetylacetonate, titanium lactate ammonium salt, titanium triethanolamine, zirconium lactate, zirconium lactate ammonium salt, aluminum lactate, aluminum trisacetylacetonate, and copper lactate; and metal alkoxides such as titanium tetraisopropoxide, titanium ethoxide, zirconium tetraisopropoxide, and aluminum trisisopropoxide.
Among these, metal chelates are preferred because the reaction is easy to control and they react quantitatively with polyvalent acid ions, and lactate chelates such as titanium lactate and zirconium lactate are more preferred from the viewpoint of solubility in aqueous media.

When obtaining fine particles of a polyvalent acid metal salt by the above method, the polyvalent acid ion may be the ion of the above-mentioned polyvalent acid. When the polyvalent acid ion is added to the aqueous medium, the polyvalent acid itself may be added, or a water-soluble polyvalent acid metal salt may be added to the aqueous medium and dissociated in the aqueous medium.
When the polyvalent acid metal salt fine particles are obtained by the above method, the number average particle size DA of the polyvalent acid metal salt fine particles can be controlled by the reaction temperature and raw material concentration when synthesizing the polyvalent acid metal salt fine particles.
The number average particle diameter DA of the polyvalent acid metal salt fine particles is preferably 3 nm to 100 nm, more preferably 5 nm to 30 nm, and even more preferably 8 nm to 20 nm.

The total content of Ca and Mg elements in the toner particles measured by an inductively coupled plasma atomic emission spectrometer is preferably 23 μmol/g or less, more preferably 20 μmol/g or less. There is no particular lower limit, but it is preferably 0 μmol/g or more, more preferably 2 μmol/g or more.
The above range indicates that there are few metal elements near the surface of the toner particles that become a source of charge leakage, and the charge retention is improved, making it easier to achieve both the charge retention and the injection charging properties.
When toner particles are produced in an aqueous medium, a calcium compound or a magnesium compound may be used as a dispersant. The above content can be controlled by the amount of the dispersant used or by removing the dispersant by washing the toner particles.

<Method of Manufacturing Toner Particles>
The method for producing toner particles will be described. The method for producing toner particles can be a known method, and a kneading and grinding method or a wet production method can be used. From the viewpoint of uniformity of particle size and shape controllability, a wet production method can be preferably used. Furthermore, examples of the wet production method include a suspension polymerization method, a dissolution suspension method, an emulsion polymerization aggregation method, and an emulsion aggregation method, and the suspension polymerization method can be preferably used.

A method for producing toner particles using a suspension polymerization method will be described below.
First, a polymerizable monomer capable of forming a binder resin and, if necessary, various other materials are mixed together, and the materials are dissolved or dispersed using a disperser to prepare a polymerizable monomer composition.
The various materials include a colorant, a wax releasing agent, a charge control agent, a polymerization initiator, and a chain transfer agent.
Examples of the dispersing machine include a homogenizer, a ball mill, a colloid mill, and an ultrasonic dispersing machine.

Next, the polymerizable monomer composition is added to an aqueous medium containing poorly water-soluble inorganic fine particles, and droplets of the polymerizable monomer composition are prepared using a high-speed disperser such as a high-speed stirrer or an ultrasonic disperser (granulation process).
Thereafter, the polymerizable monomer in the droplets of the polymerizable monomer composition is polymerized to obtain toner particles (polymerization step).
The polymerization initiator may be mixed when the polymerizable monomer composition is prepared, or may be mixed into the polymerizable monomer composition immediately before forming droplets in the aqueous medium.
Alternatively, the compound may be added in a state dissolved in the polymerizable monomer or in another solvent, as required, during or after the granulation of the droplets, that is, immediately before the start of the polymerization reaction.
After obtaining resin particles by polymerizing the polymerizable monomer, a solvent removal treatment may be carried out as necessary to obtain a dispersion of toner particles.

The weight average particle diameter (D4) of the toner particles is preferably 4.0 μm or more and 12.0 μm or less, and more preferably 5.0 μm or more and 8.0 μm or less.
The average circularity of the toner particles is preferably 0.940 or more and 0.995 or less, more preferably 0.950 or more and 0.990 or less, and even more preferably 0.970 or more and 0.990 or less.
The glass transition temperature Tg of the toner particles is preferably 40° C. or more and 70° C. or less, and more preferably 50° C. or more and 60° C. or less.

The materials constituting the toner particles will be described below.
<Binder resin>
Preferred examples of the binder resin include vinyl resins, polyester resins, etc. Examples of the vinyl resins, polyester resins and other binder resins include the following resins or polymers.

Homopolymers of styrene and its substitutes such as polystyrene and polyvinyltoluene; styrene-based copolymers such as styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, and styrene-maleic acid ester copolymer; polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, silicone resin, polyamide resin, epoxy resin, polyacrylic resin, rosin, modified rosin, terpene resin, phenolic resin, aliphatic or alicyclic hydrocarbon resin, and aromatic petroleum resin. These binder resins can be used alone or in combination.

Examples of polymerizable monomers that can be used in the production of vinyl resins include styrene-based monomers such as styrene and α-methylstyrene; acrylic acid esters such as methyl acrylate and butyl acrylate; methacrylic acid esters such as methyl methacrylate, 2-hydroxyethyl methacrylate, t-butyl methacrylate, and 2-ethylhexyl methacrylate; unsaturated carboxylic acids such as acrylic acid and methacrylic acid; unsaturated dicarboxylic acids such as maleic acid; unsaturated dicarboxylic acid anhydrides such as maleic anhydride; nitrile-based vinyl monomers such as acrylonitrile; halogen-containing vinyl monomers such as vinyl chloride; and nitro-based vinyl monomers such as nitrostyrene.
In addition to the above monomers, the monomers described above for ^P1 can also be used.

The binder resin preferably contains a carboxy group, and is preferably a resin produced using a polymerizable monomer containing a carboxy group.
Examples of the polymerizable monomer containing a carboxy group include vinylic carboxylic acids such as acrylic acid, methacrylic acid, α-ethylacrylic acid, and crotonic acid; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, and itaconic acid; and unsaturated dicarboxylic acid monoester derivatives such as succinic acid monoacryloyloxyethyl ester, succinic acid monomethacryloyloxyethyl ester, phthalic acid monoacryloyloxyethyl ester, and phthalic acid monomethacryloyloxyethyl ester.

The polyester resin may be a condensation polymer of the following carboxylic acid component and alcohol component. Examples of the carboxylic acid component include terephthalic acid, isophthalic acid, phthalic acid, fumaric acid, maleic acid, cyclohexanedicarboxylic acid, and trimellitic acid. Examples of the alcohol component include bisphenol A, hydrogenated bisphenol, an ethylene oxide adduct of bisphenol A, a propylene oxide adduct of bisphenol A, glycerin, trimethylolpropane, and pentaerythritol.
The polyester resin may be a polyester resin containing a urea group. It is preferable that the carboxyl groups at the terminals of the polyester resin are not capped.
In addition to the above monomers, the monomers described above for ^P1 can also be used.

In order to control the molecular weight of the binder resin, a crosslinking agent may be added during polymerization of the polymerizable monomer.
For example, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, divinylbenzene, bis(4-acryloxypolyethoxyphenyl)propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol #200, #400, #600 diacrylates, dipropylene glycol diacrylate, polypropylene glycol diacrylate, polyester type diacrylate (MANDA Nippon Kayaku), and those in which the above acrylates have been replaced with methacrylates.
The amount of the crosslinking agent added is preferably 0.001 parts by mass or more and 15,000 parts by mass or less based on 100 parts by mass of the polymerizable monomer.

<Release Agent>
The toner particles preferably contain a release agent. The toner particles preferably contain an ester wax having a melting point of 60° C. to 90° C. Such a wax has excellent compatibility with the binder resin and therefore is likely to provide a plasticizing effect.

Examples of ester waxes include waxes whose main component is fatty acid ester, such as carnauba wax and montan acid ester wax; fatty acid esters such as deoxidized carnauba wax from which some or all of the acid components have been deoxidized; methyl ester compounds having hydroxyl groups obtained by hydrogenating vegetable oils and fats; saturated fatty acid monoesters such as stearyl stearate and behenyl behenate; diesters of saturated fatty dicarboxylic acids and saturated fatty alcohols, such as dibehenyl sebacate, distearyl dodecane dioate, and distearyl octadecanedioate; and diesters of saturated fatty diols and saturated fatty monocarboxylic acids, such as nonanediol dibehenate and dodecanediol distearate.

Among these waxes, it is preferable to use a bifunctional ester wax (diester) having two ester bonds in the molecular structure.
The difunctional ester wax is an ester compound of a dihydric alcohol and an aliphatic monocarboxylic acid, or an ester compound of a dihydric carboxylic acid and an aliphatic monoalcohol.
Specific examples of aliphatic monocarboxylic acids include myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, melissic acid, oleic acid, vaccenic acid, linoleic acid, and linolenic acid.
Specific examples of aliphatic monoalcohols include myristyl alcohol, cetanol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, tetracosanol, hexacosanol, octacosanol, and triacontanol.

Specific examples of divalent carboxylic acids include butanedioic acid (succinic acid), pentanedioic acid (glutaric acid), hexanedioic acid (adipic acid), heptanedioic acid (pimelic acid), octanedioic acid (suberic acid), nonanedioic acid (azelaic acid), decanedioic acid (sebacic acid), dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanediic acid, phthalic acid, isophthalic acid, and terephthalic acid.
Specific examples of dihydric alcohols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, 1,18-octadecanediol, 1,20-eicosanediol, 1,30-triacontanediol, diethylene glycol, dipropylene glycol, 2,2,4-trimethyl-1,3-pentanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, spiroglycol, 1,4-phenylene glycol, bisphenol A, and hydrogenated bisphenol A.

Other usable release agents include petroleum waxes such as paraffin wax, microcrystalline wax, and petrolatum and derivatives thereof, montan wax and derivatives thereof, hydrocarbon waxes produced by the Fischer-Tropsch process and derivatives thereof, polyolefin waxes such as polyethylene and polypropylene and derivatives thereof, natural waxes such as carnauba wax and candelilla wax and derivatives thereof, higher aliphatic alcohols, and fatty acids such as stearic acid and palmitic acid.
The content of the release agent is preferably 5.0 parts by mass or more and 20.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin.

<Coloring Agent>
The toner particles may contain a colorant. The colorant is not particularly limited, and known colorants such as those shown below can be used.
Examples of yellow pigments that can be used include condensed azo compounds such as yellow iron oxide, navel yellow, naphthol yellow S, Hansa yellow G, Hansa yellow 10G, benzidine yellow G, benzidine yellow GR, quinoline yellow lake, permanent yellow NCG, and tartrazine lake, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specific examples include the following.
C.I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 155, 168, 180.

Examples of red pigments include condensed azo compounds such as red iron oxide, permanent red 4R, lithol red, pyrazolone red, watching red calcium salt, lake red C, lake red D, brilliant carmine 6B, brilliant carmine 3B, eosin lake, rhodamine lake B, and alizarin lake, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specific examples include the following.
C.I. Pigment Red 2, 3, 5, 6, 7, 23, 48:2, 48:3, 48:4, 57:1, 81:1, 122, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 254.

Examples of blue pigments include alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partial chloride, fast sky blue, copper phthalocyanine compounds such as indanthrene blue BG and derivatives thereof, anthraquinone compounds, basic dye lake compounds, etc. Specific examples include the following.
C.I. Pigment Blue 1, 7, 15, 15:1, 15:2, 15:3, 15:4, 60, 62, 66.
Examples of black pigments include carbon black and aniline black. These colorants can be used alone or in combination, or in the form of a solid solution.
The content of the colorant is preferably 3.0 parts by mass or more and 15.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin.

<External Additives>
The toner may contain various organic or inorganic fine powders as external additives to the toner particles to the extent that the above-mentioned characteristics or effects are not impaired.

The methods for measuring various physical properties are described below.
<Method of measuring weight average particle diameter (D4) and number average particle diameter (D1) of toner particles>
The weight average particle diameter (D4) and number average particle diameter (D1) of the toner particles are calculated as follows.
The measuring device used is a precision particle size distribution measuring device using the pore electrical resistance method with a 100 μm aperture tube, "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter, Inc.). The measurement conditions are set and the measurement data is analyzed using the accompanying dedicated software, "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.). The measurement is performed with an effective measurement channel count of 25,000.
The aqueous electrolyte solution used for the measurement is prepared by dissolving special grade sodium chloride in ion-exchanged water to a concentration of 1.0%, for example, "ISOTON II" (manufactured by Beckman Coulter, Inc.).
Before performing measurements and analysis, the dedicated software is set up as follows.
On the "Change standard measurement method (SOMME)" screen of the dedicated software, set the total count number in the control mode to 50,000 particles, the number of measurements to 1, and the Kd value to the value obtained using "standard particles 10.0 μm" (manufactured by Beckman Coulter, Inc.).
Press the "Threshold/Noise Level Measurement Button" to automatically set the threshold and noise level. Also, set the current to 1,600 μA, the gain to 2, the electrolyte to ISOTON II, and check "Flush aperture tube after measurement."
In the "Pulse to particle size conversion setting" screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bins, and the particle size range is set to 2 μm to 60 μm.

The specific measurement method is as follows.
(1) 200.0 mL of the electrolyte solution is placed in a 250 mL round-bottom glass beaker for use with the Multisizer 3, which is then set on the sample stand. The stirrer rod is stirred counterclockwise at 24 rotations per second. Then, dirt and air bubbles are removed from inside the aperture tube using the "aperture tube flush" function of the dedicated software.
(2) 30.0 mL of the aqueous electrolyte solution is placed in a 100 mL flat-bottom glass beaker, and 0.3 mL of a dilution of "Contaminon N" (a 10% aqueous solution of a neutral detergent for cleaning precision measuring instruments, pH 7, consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) diluted 3 times by mass with ion-exchanged water is added thereto as a dispersant.
(3) Prepare an ultrasonic disperser "Ultrasonic Dispersion System Tetra150" (manufactured by Nikkaki Bios Co., Ltd.) that has two built-in oscillators with an oscillation frequency of 50 kHz and a phase shift of 180 degrees and an electrical output of 120 W. Place 3.3 L of ion-exchanged water in the water tank of the ultrasonic disperser, and add 2.0 mL of Contaminon N to this water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid surface of the electrolytic solution in the beaker is maximized.
(5) While the electrolyte solution in the beaker in (4) is irradiated with ultrasonic waves, 10 mg of toner particles are added little by little to the electrolyte solution and dispersed. Then, ultrasonic dispersion treatment is continued for another 60 seconds. During ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be 10°C or higher and 40°C or lower.
(6) The electrolyte solution (5) in which the toner particles are dispersed is dropped into the round-bottom beaker (1) placed in the sample stand using a pipette to adjust the measurement concentration to 5%. Then, measurements are continued until the number of particles measured reaches 50,000.
(7) The measurement data is analyzed using the dedicated software provided with the device to calculate the weight average particle diameter (D4) and number average particle diameter (D1). Note that when the dedicated software is set to graph/volume %, the "average diameter" on the "analysis/volume statistics (arithmetic mean)" screen is the weight average particle diameter (D4), and when the dedicated software is set to graph/number %, the "average diameter" on the "analysis/number statistics (arithmetic mean)" screen is the number average particle diameter (D1).

<Method of measuring glass transition temperature (Tg)>
The glass transition temperature (Tg) of the binder resin, toner, etc. is measured using a differential scanning calorimeter (hereinafter also referred to as "DSC").
The measurement of the glass transition temperature by DSC is carried out in accordance with JIS K 7121 (international standard is ASTM D3418-82).
In this measurement, a "Q1000" (manufactured by TA Instruments) is used, and the melting points of indium and zinc are used for temperature correction of the device detection part, and the heat of fusion of indium is used for heat quantity correction.
The measurement is performed by precisely weighing 10 mg of a measurement sample and placing it in an aluminum pan, and using an empty aluminum pan as a reference.
In the first heating step, the measurement sample is measured while heating it from 20° C. to 200° C. at a rate of 10° C./min. Then, the sample is held at 200° C. for 10 minutes, and then cooled from 200° C. to 20° C. at a rate of 10° C./min.
After further maintaining the temperature at 20° C. for 10 minutes, the temperature is increased again from 20° C. to 200° C. at a rate of 10° C./min in a second temperature increase process.
The glass transition temperature is the midpoint glass transition temperature. In the DSC curve in the second heating process obtained under the above-mentioned measurement conditions, the glass transition temperature (Tg) is the temperature at the point where a line equidistant in the vertical direction from the line extending from each baseline on the low-temperature side and the high-temperature side of the stepwise change in glass transition temperature intersects with the curve of the stepwise change.
When the toner particles are produced in an aqueous medium, a portion of the toner particles is sampled, and the rest of the toner particles are washed and dried before the DSC measurement.

<Method for measuring average circularity>
The average circularity of the toner and toner particles is measured using a flow type particle image analyzer "FPIA-3000" (manufactured by Sysmex Corporation) under the measurement and analysis conditions during the calibration process.
The specific measurement method is as follows.
First, 20 mL of ion-exchanged water from which impurities such as solids have been removed is placed in a glass container, and about 0.2 mL of a dilution obtained by diluting "Contaminon N" (a 10% aqueous solution of a neutral detergent for cleaning precision measuring instruments, pH 7, consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) about 3 times by mass with ion-exchanged water is added thereto as a dispersant.
Further, 0.02 g of a measurement sample is added, and the mixture is dispersed for 2 minutes using an ultrasonic disperser to obtain a dispersion for measurement. At this time, the dispersion is appropriately cooled so that the temperature of the dispersion is 10° C. or higher and 40° C. or lower.
As the ultrasonic disperser, a tabletop ultrasonic cleaner disperser (e.g., "VS-150" (manufactured by Vervoclear)) with an oscillation frequency of 50 kHz and an electrical output of 150 W is used, a predetermined amount of ion-exchanged water is placed in the water tank, and about 2 mL of the Contaminon N is added to this water tank.
For the measurement, the flow type particle image analyzer equipped with "UPlanApro" (magnification 10x, numerical aperture 0.40) as the objective lens is used, and particle sheath "PSE-900A" (manufactured by Sysmex Corporation) is used as the sheath liquid.
The dispersion liquid prepared according to the above procedure is introduced into a flow type particle image analyzer, and 3,000 toner particles are counted in HPF measurement mode and total count mode.
The binarization threshold for particle analysis is set to 85%, the analyzed particle diameter is limited to a circle-equivalent diameter of 1.985 μm or more and less than 39.69 μm, and the average circularity of the toner or toner particles is obtained.
Before starting the measurement, automatic focus adjustment is performed using standard latex particles (e.g., "RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5200A" manufactured by Duke Scientific, diluted with ion-exchanged water). After that, focus adjustment is performed every 2 hours from the start of the measurement.

<Method for measuring number average particle size of primary particles of polyvalent acid metal salt fine particles>
The number average particle size of the primary particles of the polyvalent metal salt particles is measured using a scanning electron microscope "S-4800" (product name; manufactured by Hitachi, Ltd.). The toner to which the polyvalent metal salt particles have been added is observed, and the number average particle size is determined by measuring the major axis of 100 primary particles of the external additive randomly in a field of view magnified up to 50,000 times. The observation magnification is appropriately adjusted depending on the size of the polyvalent metal salt particles.

<Method for measuring normalized intensity of silicon ions present on the surface of toner particles>
The silicon ion normalized intensity on the surface of the toner particles is confirmed by a time-of-flight secondary ion mass spectrometer (TOF-SIMS). The apparatus and measurement conditions used are shown below.
The measurement is carried out on a toner from which external additives such as polyvalent acid metal salt particles have been removed by the method described below.
Measurement device: nanoTOF II (product name, manufactured by ULVAC-PHI, Inc.)
Primary ion species: Bi3 ⁺⁺
Acceleration voltage: 30 kV
Primary ion current: 0.05 pA
Repetition frequency: 8.2 kHz
・Raster mode: Unbunch
Raster size: 100 μm x 100 μm
Measurement mode: Positive
Neutralization electron gun: Used Measurement time: 600 seconds Sample preparation: Toner particles were fixed to an indium sheet Sample pretreatment: None Using ULVAC-PHI's standard software (TOF-DR), evaluation was performed based on the mass numbers of Si ions and fragment ions resulting from the resin or silane compound.
The ion intensity derived from silicon with mass number 28 (m/z 28) is divided by the total ion intensity in mass numbers 1 to 1850 to derive the silicon ion normalized intensity (m/z 28).
The fact that the normalized silicon ion intensity (m/z 28) is derived from the condensation product of the organosilicon compound is confirmed by ^29Si -NMR (solid) measurement described later. When the toner particles contain a silicon compound other than the condensation product of the organosilicon compound, the content ratio of the condensation product of the organosilicon compound to the silicon compound contained in the toner particles is derived by ^29Si -NMR (solid) measurement. Then, the value obtained by multiplying the normalized silicon ion intensity (m/z 28) by the content ratio is regarded as the intensity derived from the condensation product of the organosilicon compound.

<Method for measuring normalized intensity of silicon ions present inside toner particles>
Normally, TOF-SIMS is a surface analysis method, and data in the depth direction is about 1 nm. Therefore, the intensity inside the toner is measured after sputtering the toner with an argon gas cluster ion beam (Ar-GCIB) and scraping the surface.
After sputtering the toner particles under the conditions below, the normalized silicon ion intensity (m/z 28) measured under the same conditions as in the above "Method for measuring normalized silicon ion intensity present on the surface of a toner particle" is taken as the value of the normalized silicon ion intensity present inside the toner particle.
The sputtering conditions were as follows:
Acceleration voltage: 5 kV
Current: 6.5nA
Raster size: 600 x 600 μm
Irradiation time: 5sec/cycle
Sputtering time: 250 sec
Additionally, when a PMMA film was sputtered under the same conditions in advance to confirm the cutting depth, it was confirmed that 80 nm was removed in 250 s.

<Removal of polyvalent metal salt particles and external additives>
Add 160 g of sucrose (Kishida Chemical) to 100 mL of ion-exchanged water and dissolve in a hot water bath to prepare a concentrated sucrose solution. Place 31 g of the concentrated sucrose solution and 6 mL of Contaminon N (a 10% aqueous solution of a neutral detergent for cleaning precision measuring instruments, pH 7, consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) in a centrifuge tube to prepare a dispersion. Add 1 g of toner to this dispersion and break up the toner clumps with a spatula or the like.
The centrifugation tube is shaken for 30 minutes in a shaker ("KM Shaker" manufactured by Iwaki Sangyo Co., Ltd.) at 350 reciprocations per minute. After shaking, the solution is transferred to a glass tube for a swing rotor (50 mL) and centrifuged at 58.33 S ^-1 for 30 minutes in a centrifuge (H-9R; manufactured by Kokusan Co., Ltd.). After centrifugation, toner particles are present in the top layer in the glass tube, and external additives such as polyvalent acid metal salt fine particles are present in the aqueous solution side in the lower layer.
The toner particles in the uppermost layer are collected and filtered, and washed with 2 L of ion-exchanged water heated to 40° C., and the washed toner particles are taken out.

<Method of measuring number average molecular weight (Mn) and weight average molecular weight (Mw)>
The number average molecular weight (Mn) and weight average molecular weight (Mw) of a polymer, resin or toner particle are measured by gel permeation chromatography (GPC) as follows.
First, a sample is dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. The obtained solution is then filtered through a solvent-resistant membrane filter "Myshoridisc" (manufactured by Tosoh Corporation) with a pore size of 0.2 μm to obtain a sample solution. The sample solution is prepared so that the concentration of components soluble in THF is about 0.8 mass%. This sample solution is used to perform measurements under the following conditions.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: 7 columns of Shodex KF-801, 802, 803, 804, 805, 806, and 807 (manufactured by Showa Denko K.K.)
Eluent: tetrahydrofuran (THF)
Flow rate: 1.0mL/min
Oven temperature: 40.0°C
Sample injection volume: 0.10 mL
In calculating the molecular weight of the sample, a molecular weight calibration curve prepared using standard polystyrene resins (product names "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500", manufactured by Tosoh Corporation) is used.

<Method for extracting silane-modified resin R from toner particles>
The silane-modified resin R in the toner particles is extracted with tetrahydrofuran (THF) and separated by a solvent gradient elution method.
10.0 g of toner particles are weighed, placed in a cylindrical filter paper (Toyo Roshi No. 84) and subjected to a Soxhlet extractor. Extraction is performed for 20 hours using 200 mL of THF as a solvent, and the solid obtained by removing the solvent from the extract is the THF-soluble fraction. The THF-soluble fraction contains silane-modified resin R. This is performed multiple times to obtain the required amount of THF-soluble fraction.
For the solvent gradient elution method, a gradient preparative HPLC (Shimadzu LC-20AP high pressure gradient preparative system, Waters SunFire preparative column 50 mm φ 250 mm) is used. The column temperature is 30°C, the flow rate is 50 mL/min, and the mobile phase uses acetonitrile as a poor solvent and THF as a good solvent. 0.02 g of the THF soluble matter obtained by extraction is dissolved in 1.5 mL of THF to prepare a sample for separation.
The mobile phase starts with a composition of 100% acetonitrile, and 5 minutes after the sample injection, the ratio of THF is increased by 4% per minute until the composition of the mobile phase becomes 100% THF over 25 minutes. The components can be separated by drying the obtained fractions. This allows resin R to be obtained. Which fraction component is resin R can be determined by measuring the silicon atom content and ^13C -NMR measurement described later.

<Confirmation of the structure of the condensation product of the organosilicon compound>
The functional groups contained in the condensation product of the organosilicon compound and the polymer moieties P ¹ , L ¹ , and R ¹ to R ³ in the structure represented by formula (1) are confirmed by ¹ H-NMR analysis, ¹³ C-NMR analysis, ²⁹ Si-NMR analysis, and FT-IR analysis.
When the condensation product of the organosilicon compound is a silane-modified resin R, the measurement sample is a synthesized silane-modified resin R or a silane-modified resin R extracted from toner particles by the above-mentioned extraction method. When the condensation product of the organosilicon compound is a condensation product of a silane coupling agent, the THF-insoluble portion of the toner particles is used.
In addition, when the silicon atom in R ¹ to R ³ in the structure represented by formula (1) contains an alkoxy group or a hydroxy group, the valence of the alkoxy group or the hydroxy group relative to the silicon atom can be determined by the method shown in the "Measurement conditions for ²⁹ Si-NMR (solid)" described later.

( ^29Si -NMR (solid) measurement conditions)
Equipment: JEOL RESONANCE JNM-ECX500II
Sample tube: 3.2 mm diameter
Sample amount: 150 mg
Measurement temperature: room temperature Pulse mode: CP/MAS
Measured nuclear frequency: 97.38MHz ( ^29Si )
Reference substance: DSS (external standard: 1.534ppm)
Sample rotation speed: 10 kHz
Contact time: 10 ms
Delay time: 2s
Number of integrations: 2000 to 8000 times. By the above measurement, the abundance ratio can be obtained by peak separation and integration of multiple silane components according to the number of oxygen atoms bonded to Si by curve fitting. In this way, the valence of the alkoxy or hydroxyl groups of R ¹ to R ³ of the resin represented by formula (1) relative to the silicon atom can be confirmed.
Those having at least one of the following M unit, D unit, or T unit structures can be considered to be condensation products of organosilicon compounds. Those having the following Q unit structure can be considered to be silicon compounds other than the condensation products of organosilicon compounds.
At least one of the R's in each unit below is a carbon atom. The other R's are any groups, such as a hydrogen atom, a halogen atom, an alkyl group having 1 or more carbon atoms, an alkoxy group having 1 or more carbon atoms, an aryl group having 6 or more carbon atoms, or a hydroxy group, as with R ¹ to ^R 3 in formula (1).

The structures of P ¹ , L ¹ and R ¹ to R ³ in the silane-modified resin R represented by formula (1) can be confirmed by ¹³ C-NMR (solid) measurement. The measurement conditions are as follows.
( ^13C -NMR (solid) measurement conditions)
Equipment: JEOL RESONANCE JNM-ECX500II
Sample tube: 3.2 mm diameter
Sample amount: 150 mg
Measurement temperature: room temperature Pulse mode: CP/MAS
Measurement nuclear frequency: 123.25MHz ( ^13C )
Reference substance: Adamantane (external standard: 29.5ppm)
Sample rotation speed: 20 kHz
Contact time: 2 ms
Delay time: 2s
Number of accumulations: 1024 Various peaks are separated according to the types of P ¹ , L ¹ and R ¹ to R ³ in formula (1), and each peak is identified to determine the types of P ¹ , L ¹ and R ¹ to R ³ .

<Measurement of Polymerization Conversion Rate of Polymerizable Monomer>
The polymerization conversion rate of the polymerizable monomer is measured by gas chromatography (GC) as follows.
2.55 mg of DMF (dimethylformamide) is added to 100 ml of acetone to prepare a solvent containing an internal standard. Next, 0.2 g of the polymerizable monomer composition dispersion is precisely weighed and dissolved in the above solvent to make 10 ml of solution. After placing it in an ultrasonic shaker for 30 minutes, it is left for 1 hour. Next, it is filtered through a 0.5 μm membrane filter, and 4 μl of the filtrate is analyzed by gas chromatography.
A calibration curve is prepared in advance to determine the mass ratio/area ratio of the polymerizable vinyl monomer to the internal standard DMF. The amount of unreacted polymerizable monomer is calculated from the obtained chromatogram to determine the polymerization conversion rate.
The measuring device and measuring conditions are as follows.
GC: Shimadzu Corporation GC-14A
Column: J&W Scientific DB-WAX (249 μm x 0.25 μm x 30 m)
Carrier gas: _N2
Oven: (1) Hold at 70°C for 2 minutes, (2) Heat to 220°C at 5°C/min. Inlet: 200°C
Split ratio: 1:20
Detector: 200°C (FID)

<Measurement of the Total Content of Ca Element and Mg Element in Toner Particles>
The total content of Ca and Mg elements derived from the dispersant etc. is quantified by an inductively coupled plasma atomic emission spectrometer (ICP-AES (manufactured by Seiko Instruments Inc.)).
As a pretreatment, 100.0 mg of the toner particles are subjected to acid decomposition using 8.00 ml of 60% nitric acid (manufactured by Kanto Chemical, for atomic absorption spectrometry).
During acid decomposition, the sample is treated in a sealed container at an internal temperature of 220° C. for 1 hour using a microwave high-power sample pretreatment device ETHOS1600 (Milestone General Co., Ltd.) to prepare a polyvalent metal element-containing solution sample.
Then, ultrapure water is added to make the total weight 50.00 g to obtain the measurement sample. A calibration curve is created for each polyvalent metal element, and the amount of metal contained in each sample is quantified. Note that ultrapure water is added to 8.00 ml of nitric acid to make a total weight of 50.00 g, and the blank metal amount is subtracted from the blank metal amount.

The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is in no way limited thereto. Parts used in the examples are by weight unless otherwise specified.

<Production Example of Resin R1>
The following materials were charged into an autoclave equipped with a pressure reducing device, a water separating device, a nitrogen gas introducing device, a temperature measuring device, and a stirrer, and a reaction was carried out under a nitrogen atmosphere at normal pressure and 200° C. for 20 hours.
Alcohol component: 80.9 parts (bisphenol A-propylene oxide 2.0 mol adduct)
Acid component 1 (terephthalic acid): 16.1 parts Acid component 2 (isophthalic acid): 16.1 parts Tetrabutoxytitanate: 0.2 parts Thereafter, the following materials were added and reacted at 220° C. for 3 hours.
Acid or alcohol component 3 (trimellitic acid): 0.4 parts Tetrabutoxytitanate: 0.3 parts The reaction was further carried out for 2 hours under a reduced pressure of 10 to 20 mmHg. The resulting resin was dissolved in chloroform, and the solution was dropped into ethanol to cause reprecipitation and filtration, thereby obtaining a polyester resin.
The carboxy group in the obtained polyester resin and the amino group in the aminosilane were amidated to produce Resin R1 as follows.
100.0 parts of the polyester was dissolved in 400.0 parts of N,N-dimethylacetamide, and the following materials were added and stirred at room temperature for 5 hours. After the reaction was completed, the solution was dropped into methanol for reprecipitation and filtration to obtain resin R1.
Silane compound (3-aminopropyltrimethoxysilane): 0.2 parts Triethylamine: 0.3 parts Condensing agent (amidating agent): 0.3 parts [DMT-MM: 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride]
The structure and physical properties of the obtained resin R1 are shown in Table 1.

<Production Example of Resin R2>
The following materials were charged into an autoclave equipped with a pressure reducing device, a water separating device, a nitrogen gas introducing device, a temperature measuring device, and a stirrer, and a reaction was carried out under a nitrogen atmosphere at normal pressure and 200° C. for 5 hours.
Alcohol component: 93.2 parts (bisphenol A-propylene oxide 2.0 mol adduct)
Acid component 1 (terephthalic acid): 11.2 parts Acid component 2 (isophthalic acid): 11.2 parts Tetrabutoxytitanate: 0.2 parts Thereafter, the following materials were added and reacted at 220° C. for 3 hours.
Tetrabutoxytitanate: 0.3 parts In order to obtain a lower molecular weight product, the reaction pressure, reaction temperature and reaction time were appropriately adjusted.
The carboxy group in the obtained polyester and the amino group in the aminosilane were amidated to produce Resin R2 as follows.
100.0 parts of the polyester was dissolved in 400.0 parts of N,N-dimethylacetamide, and the following materials were added and stirred at room temperature for 5 hours. After the reaction was completed, the solution was dropped into methanol for reprecipitation and filtration to obtain resin R2.
Silane compound (3-aminopropylmethyldimethoxysilane): 1.2 parts Triethylamine: 2.4 parts Condensing agent (amidating agent): 2.4 parts [DMT-MM: 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride]
The structure and physical properties of the obtained resin R2 are shown in Table 1.

<Production Examples of Resins R3 to R5 and R7>
Resins R3 to R5 and Resin R7 were obtained in the same manner as in the production example of Resin R2, except that the silane compound, triethylamine and condensing agent in the production example of Resin R2 were changed as shown in Table 1.
The structure and physical properties of the resulting resin are shown in Table 1.

<Production Example of Resin R6>
100.0 parts of propylene glycol monomethyl ether was heated while replacing with nitrogen, and refluxed at a liquid temperature of 120° C. or higher, to which a mixture of the following materials was added dropwise over a period of 3 hours.
Styrene: 64.1 parts Butyl acrylate: 30.9 parts Acrylic acid: 5.0 parts tert-butyl peroxybenzoate: 1.0 part (organic peroxide polymerization initiator, manufactured by NOF Corporation, product name: Perbutyl Z)
After the dropwise addition was completed, the solution was stirred for 3 hours, and then distilled at normal pressure while increasing the liquid temperature to 170° C. After the liquid temperature reached 170° C., the pressure was reduced to 1 hPa, and distillation was performed for 1 hour to remove the solvent, obtaining a resin solid. The resin solid was dissolved in tetrahydrofuran, reprecipitated with n-hexane, and the precipitated solid was filtered off to obtain a styrene-acrylic resin.
The carboxy group in the obtained styrene-acrylic resin and the amino group in the aminosilane were amidated to produce Resin R6 as follows.
100.0 parts of the styrene-acrylic acid copolymer was dissolved in 400.0 parts of N,N-dimethylacetamide, and the following materials were added and stirred at room temperature for 5 hours. After the reaction was completed, the solution was dropped into methanol, reprecipitated, and filtered to obtain silane-modified resin R6.
Silane compound (3-aminopropyltrimethylsilane): 1.0 part Triethylamine: 2.7 parts Condensing agent: 2.7 parts [DMT-MM: 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride]
The structure and physical properties of the obtained resin R6 are shown in Table 1.

表中、Ｐ１、Ｌ１及びＲ１～Ｒ３は、式（１）のＰ^１、Ｌ^１及びＲ^１～Ｒ^３に相当する。表中Ｒ５は、式（２）中のＲ^５に相当し、プロピル基を示す。Ｍｅはメチル基を示し、Ｅｔはエチル基を示す。
表中の略称は以下の通り。
ＢＰＡ（ＰＯ）：ビスフェノールＡ－プロピレンオキサイド２．０モル付加物
ＴＰＡ：テレフタル酸
ＩＰＡ：イソフタル酸
Ｓｔ：スチレン
ＢＡ：アクリル酸ブチル
ＡＡ：アクリル酸

In the table, P1, L1, and R1 to R3 correspond to P ¹ , L ^1, and R ¹ to R ³ in formula (1). R5 in the table corresponds to R ⁵ in formula (2) and represents a propyl group. Me represents a methyl group, and Et represents an ethyl group.
The abbreviations in the table are as follows:
BPA(PO): Bisphenol A-propylene oxide 2.0 mole adduct TPA: Terephthalic acid IPA: Isophthalic acid St: Styrene BA: Butyl acrylate AA: Acrylic acid

<Production Example of Toner Particle 1>
(Preparation of Polymerizable Monomer Composition 1)
The above materials were put into an attritor (manufactured by Nippon Coke & Engineering Co., Ltd.), and further dispersed at 220 rpm for 5.0 hours using zirconia particles having a diameter of 1.7 mm, and then the zirconia particles were removed to prepare a colorant dispersion in which the pigment was dispersed.
The following materials were then added to the colorant dispersion:
Styrene 15.0 parts n-butyl acrylate 25.0 parts hexanediol diacrylate 0.5 parts polyester resin 5.0 parts (condensation polymer of terephthalic acid and 2 moles of propylene oxide adduct of bisphenol A, weight average molecular weight Mw is 10000, acid value is 8.2 mgKOH/g)
Release agent (hydrocarbon wax, melting point: 79° C.) 5.0 parts Plasticizer (ethylene glycol distearate) 15.0 parts Next, in the dissolving and dispersing step, the above materials were kept at 65° C. and uniformly dissolved and dispersed at 500 rpm using a T.K. homomixer to prepare a polymerizable monomer composition.

(Preparation of aqueous medium 1)
11.2 parts of sodium phosphate (12-hydrate) was added to a reaction vessel containing 390.0 parts of ion-exchanged water, and the mixture was kept at 65°C for 1.0 hours while purging with nitrogen. A T.K. homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) was used to stir at 12000 rpm. While maintaining stirring, an aqueous calcium chloride solution in which 7.4 parts of calcium chloride (2-hydrate) was dissolved in 10.0 parts of ion-exchanged water was added to the reaction vessel all at once to prepare an aqueous medium containing a dispersion stabilizer. Furthermore, 1.0 mol/L of hydrochloric acid was added to the aqueous medium in the reaction vessel to adjust the pH to 6.0, and aqueous medium 1 was prepared.

(Granulation process)
While maintaining the temperature of the aqueous medium 1 at 70° C. and the rotation speed of the stirring device at 12,500 rpm, the polymerizable monomer composition was charged into the aqueous medium 1, and 8.0 parts of t-butyl peroxypivalate as a polymerization initiator was added. Granulation was continued for 10 minutes while maintaining the stirring device at 12,500 rpm.

(Polymerization step A)
The high-speed stirrer was changed to a stirrer equipped with a propeller stirring blade, and polymerization was carried out for 5.0 hours while stirring at 200 rpm and maintaining the temperature at 70°C.

(Polymerization step B)
Continuing from the polymerization step A, the temperature was further raised to 85° C. and heated for 2.0 hours to carry out a polymerization reaction. Further, 0.03 parts of 3-methacryloxypropyltrimethoxysilane (M1) was added and stirred for 5 minutes, and then a 1 mol/L aqueous sodium hydroxide solution was added to adjust the pH to 9.0.
The temperature was then increased to 98° C. and heated for 3.0 hours to remove residual monomers. Thereafter, the temperature was decreased to 55° C., and the temperature was maintained at 55° C. for 5.0 hours while stirring was continued. The temperature was then decreased to 25° C. Ion-exchanged water was added to adjust the toner particle concentration in the dispersion to 30.0%, and toner particle dispersion 1 in which toner particles 1 were dispersed was obtained.

(Washing process)
The toner particle dispersion 1 was adjusted to pH 1.5 with 1 mol/L hydrochloric acid and stirred for 1.0 hour, and then washed with ion-exchanged water, filtered and dried to obtain toner particles 1.
The silane compounds used are shown in Table 2, and the physical properties of the toner particles 1 obtained are shown in Table 3.

<Production Example of Toner Particle 2>
Toner particles 2 are obtained in the same manner as in the production example of toner particles 1, except that the amount of 3-methacryloxypropyltrimethoxysilane (M1) added is changed to 0.01 parts.
The silane compounds used are shown in Table 2, and the physical properties of the toner particles 2 obtained are shown in Table 3.

<Production Example of Toner Particle 3>
A mixture of 15.0 parts of ion-exchanged water adjusted to pH 4.0 by adding 1 mol/L hydrochloric acid and 0.15 parts of 3-methacryloxypropyltrimethoxysilane (M1) was mixed using a stirrer until a homogeneous phase was obtained, thereby obtaining a monomer hydrolyzed liquid 1.
Toner particles 3 were obtained in the same manner as in the production example of toner particles 1, except that, after the completion of the polymerization step A, the entire amount of monomer hydrolyzed liquid 1 was added and stirred for 5 minutes, and then a 1 mol/L aqueous sodium hydroxide solution was added to adjust the pH to 9.0, and 3-methacryloxypropyltrimethoxysilane (M1) was not added in the polymerization step B.
The silane compounds used are shown in Table 2, and the physical properties of the toner particles 3 obtained are shown in Table 3.

<Production Example of Toner Particle 4>
In the production example of toner particle 1, after the completion of the polymerization step A, 0.15 parts of 3-methacryloxypropyltrimethoxysilane (M1) was added and stirred for 5 minutes, and then a 1 mol/L aqueous sodium hydroxide solution was added to adjust the pH to 9.0, and toner particle 4 was obtained in the same manner as in the production example of toner particle 1, except that 3-methacryloxypropyltrimethoxysilane (M1) was not added in the polymerization step B.
The silane compounds used are shown in Table 2, and the physical properties of the toner particles 4 obtained are shown in Table 3.

<Production Example of Toner Particle 5>
A mixture of 0.03 parts of ion-exchanged water adjusted to pH 4.0 by adding 1 mol/L hydrochloric acid and 0.02 parts of methyltrimethoxysilane (M7) was mixed using a stirrer until a homogeneous phase was obtained, thereby obtaining a monomer hydrolyzed liquid 2.
Toner particles 5 are obtained in the same manner as in the production example of toner particles 2, except that the entire amount of monomer hydrolyzed liquid 2 is added immediately after the temperature is lowered to 55°C.
The silane compounds used are shown in Table 2, and the physical properties of the toner particles 5 obtained are shown in Table 3.

<Production Example of Toner Particle 6>
Toner particles 6 were obtained in the same manner as in the production example of toner particles 1, except that 0.01 parts of 3-methacryloxypropyltrimethoxysilane (M1) was changed to 0.40 parts of 3-methacryloxypropyltris(trimethylsiloxy)silane (M2).
The silane compounds used are shown in Table 2, and the physical properties of the toner particles 6 obtained are shown in Table 3.

<Production Example of Toner Particle 7>
Toner particles 7 were obtained in the same manner as in the production example of toner particles 6, except that in the production example of toner particles 6, the stirring time from the addition of 3-methacryloxypropyltris(trimethylsiloxy)silane (M2) until the adjustment to pH = 9.0 was changed to 60 minutes.
The silane compounds used are shown in Table 2, and the physical properties of the toner particles 7 obtained are shown in Table 3.

<Production Example of Toner Particle 8>
Toner particles 8 were obtained in the same manner as in the production example of toner particles 6, except that in the production example of toner particles 6, the addition of 0.40 parts of 3-methacryloxypropyltris(trimethylsiloxy)silane (M2) was changed to after the temperature was lowered to 55° C. in the polymerization step B, and after stirring for 60 minutes after the addition, a 1 mol/L aqueous sodium hydroxide solution was added to adjust the pH to 9.0, and then the temperature was maintained at 55° C. for 4.0 hours while continuing to stir.
The silane compounds used are shown in Table 2, and the physical properties of the toner particles 8 obtained are shown in Table 3.

<Production Examples of Toner Particles 9 to 12>
Toner particles 9 to 12 were obtained in the same manner as in the production example of toner particles 1, except that 3-methacryloxypropyltrimethoxysilane (M1) was changed to that shown in Table 3 in the production example of toner particles 1.
The silane compounds used are shown in Table 2, and the physical properties of the resulting toner particles 9 to 12 are shown in Table 3.

<Production Example of Toner Particles 13>
(Preparation of aqueous medium 2)
10.2 parts of magnesium chloride was added to a reaction vessel containing 250.0 parts of ion-exchanged water, and the mixture was kept at 65°C for 1.0 hours while purging with nitrogen. A T.K. homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) was used to stir at 12000 rpm. While maintaining stirring, an aqueous calcium chloride solution in which 6.2 parts of sodium hydroxide was dissolved in 50.0 parts of ion-exchanged water was added to the reaction vessel all at once to prepare an aqueous medium containing a dispersion stabilizer. Furthermore, 1.0 mol/L of hydrochloric acid was added to the aqueous medium in the reaction vessel to adjust the pH to 6.0, and aqueous medium 2 was prepared.
Toner particles 13 are obtained in the same manner as in the production example of toner particles 1, except that the aqueous medium 1 in the production example of toner particles 1 is changed to the aqueous medium 2.
The silane compounds used are shown in Table 2, and the physical properties of the toner particles 13 obtained are shown in Table 3.

<Production Example of Toner Particles 14>
Toner particles 14 were obtained in the same manner as in the production example of toner particles 13, except that the amount of magnesium chloride was changed to 12.2 parts in the production example of toner particles 13. The physical properties of the obtained toner particles 14 are shown in Table 3.

<Production Example of Toner Particles 15>
Toner particles 15 were obtained in the same manner as in the production example of toner particles 1, except that 5.0 parts of the polyester resin in the production example of toner particles 1 was changed to 4.5 parts of polyester resin and 1.00 parts of resin R1. The physical properties of the obtained toner particles 15 are shown in Table 3.

<Production Examples of Toner Particles 16 to 21, and 25>
Toner particles 16 to 21 and 25 were obtained in the same manner as in the production example of toner particles 15, except that resin R1 in the production example of toner particles 15 was changed to any one of resins R2 to R7 in the number of parts as shown in Table 3. The physical properties of the obtained toner particles 16 to 21 and 25 are shown in Table 3.

<Production Example of Toner Particles 22>
<Preparation of Binder Resin Particle Dispersion>
89.5 parts of styrene, 9.2 parts of butyl acrylate, 1.3 parts of acrylic acid as a carboxyl group-imparting monomer, and 3.2 parts of n-lauryl mercaptan were mixed and dissolved in the solution, and an aqueous solution in which 1.5 parts of NEOGEN RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was dissolved in 150 parts of ion-exchanged water was added to the solution and dispersed.
While slowly stirring for another 10 minutes, an aqueous solution in which 0.3 parts of potassium persulfate was dissolved in 10 parts of ion-exchanged water was added. After nitrogen replacement, emulsion polymerization was carried out for 6 hours at 70° C. After the polymerization was completed, the reaction solution was cooled to room temperature, and ion-exchanged water was added to obtain a binder resin particle dispersion having a solid content concentration of 12.5 mass % and a volume-based median diameter of 0.2 μm.
The binder resin constituting the resin particles had a carboxyl group derived from acrylic acid and had a glass transition temperature of 57°C.

<Preparation of Wax Dispersion>
100 parts of a diester compound (ethylene glycol distearate), 30 parts of a paraffin wax "HNP-9" (manufactured by Nippon Seiro Co., Ltd., melting point 75°C) as a release wax, and 20 parts of NEOGEN RK were mixed with 400 parts of ion-exchanged water. After that, the mixture was dispersed for about 1 hour using a wet jet mill JN100 (manufactured by Jokou Co., Ltd.) to obtain a wax dispersion.

<Preparation of Colorant Dispersion>
As colorants, C.I. Pigment Blue 15:3 (100 parts) and 15 parts of NEOGEN RK were mixed with 885 parts of ion-exchanged water, and dispersed for about 1 hour using a wet jet mill JN100 to obtain a colorant dispersion.

265 parts of the obtained binder resin particle dispersion, 80 parts of the wax dispersion, and 10 parts of the colorant dispersion were dispersed using a homogenizer (Ultra Turrax T50 manufactured by IKA Corporation). The temperature inside the container was adjusted to 30° C. while stirring, and a 1 mol/L aqueous sodium hydroxide solution was added to adjust the pH to 8.0.
As a flocculant, an aqueous solution of 0.5 parts of magnesium chloride dissolved in 10 parts of ion-exchanged water was added over 10 minutes under stirring at 30°C. After leaving it for 3 minutes, the temperature was raised to 50°C to generate associated particles. In this state, the particle size of the associated particles was measured using a "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter, Inc.). When the weight average particle size reached 6.5 μm, 3.0 parts of sodium chloride and 8.0 parts of Neogen RK were added to stop particle growth.
Thereafter, the mixture was heated to 95° C. and stirred while being held at this state to fuse and spheronize the associated particles. When the average circularity reached 0.980, the mixture was cooled to 80° C. and held at 80° C. Ice water was added thereto to rapidly cool the mixture from the rapid cooling start temperature of 80° C. to the rapid cooling end temperature of 30° C. at a rapid cooling rate of 3° C./sec.
Thereafter, the temperature was raised again to 55° C., 0.40 parts of 3-methacryloxypropyltris(trimethylsiloxy)silane (M2) was added, and the mixture was stirred for 60 minutes. Thereafter, a 1 mol/L aqueous sodium hydroxide solution was added to adjust the pH to 9.0, and the mixture was kept at 55° C. for 4.0 hours while continuing to stir, and then the temperature was lowered to 25° C. to obtain a toner particle dispersion liquid 22.
The pH of the obtained toner particle dispersion 2 was adjusted to 1.5 with 1 mol/L hydrochloric acid and stirred for 1.0 hour, and then the mixture was washed with ion-exchanged water, filtered and dried to obtain toner particles 22.
The silane compounds used are shown in Table 2, and the physical properties of the toner particles 22 obtained are shown in Table 3.

<Production Example of Toner Particles 23>
Binder resin (styrene-n-butyl acrylate copolymer): 100.0 parts (styrene-n-butyl acrylate copolymer ratio (mass ratio) is 75:25, peak molecular weight (Mp) is 22,000, weight average molecular weight (Mw) is 35,000, Mw/Mn=2.4, Mn represents number average molecular weight.)
・6.3 parts of C.I. Pigment Blue 15:3・5.0 parts of release agent (hydrocarbon wax, melting point 79 ° C.)・5.0 parts of plasticizer (ethylene glycol distearate) The above materials were premixed with an FM mixer (manufactured by Nippon Coke & Engineering Co., Ltd.), and then melt-kneaded with a twin-screw kneader (PCM-30 type manufactured by Ikegai Iron Works, Ltd.) to obtain a kneaded product. The kneaded product obtained was cooled, coarsely pulverized with a hammer mill (manufactured by Hosokawa Micron Corporation), and then pulverized with a mechanical pulverizer (T-250 manufactured by Turbo Kogyo Co., Ltd.) to obtain a finely pulverized powder.
The resulting finely pulverized powder was reslurried in aqueous medium 1 to form a dispersion again, and the temperature was raised again to 55° C. Then, 0.40 parts of 3-methacryloxypropyltris(trimethylsiloxy)silane (M2) was added and stirred for 60 minutes. Thereafter, a 1 mol/L aqueous sodium hydroxide solution was added to adjust the pH to 9.0, and the mixture was kept at 55° C. for 4.0 hours while continuing to stir, and then the temperature was lowered to 25° C. to obtain toner particle dispersion 23.
The pH of the obtained toner particle dispersion 23 was adjusted to 1.5 with 1 mol/L hydrochloric acid and stirred for 1.0 hour, and then the mixture was washed with ion-exchanged water, filtered, and dried to obtain toner particles 23.
The silane compounds used are shown in Table 2, and the physical properties of the toner particles 23 obtained are shown in Table 3.

<Production Example of Toner Particles 24>
Toner particles 24 are obtained in the same manner as in the production example of toner particles 3, except that in the production example of toner particles 3, the amount of 3-methacryloxypropyltrimethoxysilane (M1) is changed to 0.50 parts.
The silane compounds used are shown in Table 2, and the physical properties of the toner particles 24 obtained are shown in Table 3.

<Production Example of Toner Particles 26>
Toner particles 26 are obtained in the same manner as in the production example of toner particles 1, except that 3-methacryloxypropyltrimethoxysilane (M1) is not added in the polymerization step B.
The physical properties of the obtained toner particles 26 are shown in Table 3. The normalized strength of the toner particles 26 in Table 3 is a value derived from the base strength.

<Production Example of Toner Particles 27>
Toner particles 27 were obtained in the same manner as in the production example of toner particles 24, except that 0.40 parts of 3-methacryloxypropyltrimethoxysilane (M1) was replaced with 3-methacryloxypropyltris(trimethylsiloxy)silane (M2).
The silane compounds used are shown in Table 2, and the physical properties of the toner particles 27 obtained are shown in Table 3.

<Production Example of Toner Particles 28>
Toner particles 28 were obtained in the same manner as in the production example of toner particles 1, except that in the preparation of polymerizable monomer composition 1, 0.03 parts of silica particles (Snowtex PS (manufactured by Nissan Chemical Industries, Ltd.)) were added, and in the polymerization step B, 3-methacryloxypropyltrimethoxysilane (M1) was not added.
The physical properties of the resulting toner particles 28 are shown in Table 3.

表中、＊１は、トナー粒子の飛行時間型二次イオン質量分析計（ＴＯＦ－ＳＩＭＳ）におけるケイ素イオン（ｍ／ｚ２８）の規格化強度を示す。＊２は、トナー粒子を上記（Ａ）条件でスパッタした後のケイ素イオン（ｍ／ｚ２８）の規格化強度を示す。
「縮合の有無」は、トナー粒子が有機ケイ素化合物の縮合生成物を含有するか否かを示している。
規格化強度に関し、例えば、「２．１１．Ｅ－０３」との記載は、「２．１１×１０^－３」であることを示す。

In the table, *1 indicates the normalized intensity of silicon ions (m/z 28) in a time-of-flight secondary ion mass spectrometer (TOF-SIMS) of the toner particles, and *2 indicates the normalized intensity of silicon ions (m/z 28) after the toner particles are sputtered under the above condition (A).
"Condensation or not" indicates whether the toner particles contain a condensation product of an organosilicon compound.
Regarding the normalized intensity, for example, "2.11.E-03" indicates that it is "2.11×10 ^-3 ."

<Production Example of Toner 1>
(Preparation of Toner Particle Dispersion)
The toner particles 1 were reslurried in ion-exchanged water to obtain a toner particle dispersion 1 having a toner particle concentration of 20% by mass.
(Addition of polyvalent metal salt particles)
The following materials were weighed and placed in a reaction vessel and mixed using a propeller stirring blade.
Sodium phosphate (12-hydrate) 0.9 parts Titanium lactate (TC-310, manufactured by Matsumoto Fine Chemical Co., Ltd.) 1.0 part Toner particle dispersion 1 500.0 parts Next, the pH of the resulting mixture was adjusted to 7.0, and the temperature of the mixture was increased to 55° C., and the mixture was maintained for 1 hour while being mixed using a propeller stirring blade.
Thereafter, the pH was adjusted to 9.5 using a 1 mol/L aqueous NaOH solution, and the temperature was kept at 50° C. for 2 hours with stirring.
The pH was adjusted to 1.5 with 1 mol/L hydrochloric acid and stirred for 1 hour, after which the mixture was washed with ion-exchanged water, filtered and dried, and the resulting finely pulverized powder was classified using a multi-division classifier utilizing the Coanda effect to obtain toner 1.
Observation with a SEM revealed that the number-average particle size of the titanium phosphate compound was 11 nm. Calculation of the amount of the titanium phosphate compound present with fluorescent X-rays revealed that it was 0.2 parts per 100 parts of the toner particles.
The physical properties of the obtained toner 1 are shown in Table 4.

<Production Examples of Toners 2 to 5, 9 to 18, 21 to 31, 35 to 37, 39, and 40>
Toners 2 to 5, 9 to 18, 21 to 31, 35 to 37, 39, and 40 were obtained in the same manner as in Production Example of Toner 1, except that the type of toner particles, the number of parts of the polyvalent acid source, and the type and number of parts of the metal source were changed as shown in Table 4. The amount of polyvalent acid metal salt fine particles present on the surface of the obtained toners was as shown in Table 4.
The physical properties of the obtained toner are shown in Table 4.

<Production Example of Toner 6>
Toner particles 1: 0.5 parts of titanium oxide fine particles were added as a metal source to 100.0 parts of the toner particles, and mixed using an FM mixer (manufactured by Nippon Coke & Co., Ltd.) to obtain toner 6.
The physical properties of the obtained toner 6 are shown in Table 4.

<Production Examples of Toners 7, 8, 32, 33, and 38>
Toners 7, 8, 32, 33 and 38 were obtained in the same manner as in the production example of toner 6, except that the toner particles and the types and parts of the metal source were changed as shown in Table 4.
The physical properties of the obtained toner are shown in Table 4.

<Production Example of Toner 19>
Ion-exchanged water 100.0 parts Sodium sulfate 4.8 parts After mixing the above, 10.0 parts of titanium lactate (TC-310, Matsumoto Fine Chemical Co., Ltd.) was added at room temperature while stirring at 13,000 rpm using a T.K. homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). 1 mol/L hydrochloric acid was added to adjust the pH to 7.0.
The solid content was then separated by centrifugation. The process of dispersing again in ion-exchanged water and separating the solid content by centrifugation was repeated three times to remove ions such as sodium. The resultant was dispersed again in ion-exchanged water and dried by spray drying to obtain titanium sulfate compound microparticles 1 having a number-average particle size of 99 nm.
Toner particles 1: 100.0 parts, titanium sulfate compound fine particles 1: 0.5 parts were added, and mixed using an FM mixer (manufactured by Nippon Coke & Co., Ltd.) to obtain toner 19.
The physical properties of the obtained toner 19 are shown in Table 4.

<Production Example of Toner 20>
Ion-exchanged water 100.0 parts Sodium carbonate 3.6 parts After mixing the above, 10.0 parts of titanium lactate (TC-310, Matsumoto Fine Chemical Co., Ltd.) was added at room temperature while stirring at 13,000 rpm using a T.K. homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). 1 mol/L hydrochloric acid was added to adjust the pH to 7.0.
The solid content was then separated by centrifugation. The process of dispersing again in ion-exchanged water and separating the solid content by centrifugation was repeated three times to remove ions such as sodium. The resultant was dispersed again in ion-exchanged water and dried by spray drying to obtain titanium carbonate compound microparticles 1 having a number-average particle size of 91 nm.
Toner particles 1: 100.0 parts were added titanium sulfate compound fine particles 1: 0.5 parts, and mixed using an FM mixer (manufactured by Nippon Coke & Co., Ltd.) to obtain toner 20.
The physical properties of the obtained toner 20 are shown in Table 4.

<Production Example of Toner 34>
Toner particles 1: 0.5 parts of silicon dioxide was added to 100.0 parts of the toner particles, and mixed using an FM mixer (manufactured by Nippon Coke & Co., Ltd.) to obtain toner 34.

表中、ＤＡは、多価酸金属塩微粒子の個数平均粒径を示す。Ｘは、トナー粒子１００部に対する多価酸金属塩微粒子の量を示す。

In the table, DA represents the number average particle diameter of the fine particles of a polyvalent acid metal salt, and X represents the amount of the fine particles of a polyvalent acid metal salt per 100 parts of toner particles.

Example 1
First, a modified Canon laser beam printer LBP652C was prepared as an electrophotographic apparatus. The modified parts were connected to an external high voltage power source so that an arbitrary potential difference could be provided between the charging blade and the charging roller, and the process speed was set to 200 mm/sec.
Next, the process cartridge in which the toner 1 was filled in the LBP652C cartridge and the electrophotographic apparatus were left to stand in a normal temperature and humidity environment (25° C./50% RH) for 48 hours in order to acclimate them to the measurement environment.

<Evaluation of Charge Retention Property>
First, an all-black image was output by setting the potential difference between the charging blade and the charging roller to −400 V. During image formation, the device was stopped, the process cartridge was removed from the main body, and the charge amount of the toner on the photosensitive drum was evaluated using a charge amount distribution measuring device, Espart Analyzer EST-1 (manufactured by Hosokawa Micron Corporation).
The charge retention was evaluated by comparing the charge amount on the developing roller in the above charge injection evaluation with the charge amount on the photosensitive drum in this evaluation.
In this evaluation, the higher the charge retention, the less likely the charge is to leak during the development process, and therefore the higher the charge amount is maintained. In other words, the smaller the value, the better the charge retention.
The evaluation results of Example 1 are shown in Table 5.
<Charge retention>
A: The charge amount difference between the developing roller and the photosensitive drum is 3 μC/g or less. B: The charge amount difference between the developing roller and the photosensitive drum is more than 3 μC/g and less than 6 μC/g. C: The charge amount difference between the developing roller and the photosensitive drum is more than 6 μC/g and less than 10 μC/g. D: The charge amount difference between the developing roller and the photosensitive drum is more than 10 μC/g.

<Charge injection property (amount of injected charge)>
First, an all-white image was output by setting the potential difference between the charging blade and the charging roller to 0 V. During image formation, the device was stopped, the process cartridge was removed from the main body, and the charge amount and charge amount distribution of the toner on the developing roller were evaluated using a charge amount distribution measuring device, Espart Analyzer EST-1 (manufactured by Hosokawa Micron Corporation).
Next, the potential difference between the charging blade and the charging roller was set to -400 V, and the same evaluation was carried out.
The injected charge amount and the injected charge amount distribution were evaluated from the change in the charge amount ΔQ/M (unit: μC/g) and the change in the charge amount distribution when the potential difference was 0 V and −400 V.
As for the charge amount distribution, the evaluation criterion was how many times the half-value width of the charge amount distribution at -400V was compared with the half-value width of the charge amount distribution at 0V.
In this standard, the smaller the magnification, the sharper the charge distribution becomes, indicating an excellent charging state.
In this evaluation, the higher the charge injection property, the larger the charge difference (ΔQ/M) because the charge amount changes according to the potential difference. At the same time, a uniform charge amount distribution, which is one of the excellent characteristics of injection charge, can be obtained.
The evaluation results of Example 1 are shown in Table 5.
<Charge injection property>
A: ΔQ/M is greater than 20 μC/g B: ΔQ/M is greater than 10 μC/g and less than 20 μC/g C: ΔQ/M is greater than 5 μC/g and less than 10 μC/g D: ΔQ/M is less than 5 μC/g <Injected charge distribution>
A: When −400 V is used, the half-width of the charge distribution is 0.70 times or less compared to when it is 0 V. B: When −400 V is used, the half-width of the charge distribution is more than 0.70 times and less than 0.80 times compared to when it is 0 V. C: When −400 V is used, the half-width of the charge distribution is more than 0.80 times and less than 0.90 times compared to when it is 0 V. D: When −400 V is used, the half-width of the charge distribution is more than 0.90 times compared to when it is 0 V.

<Evaluation of charge injection (amount of injected charge) at low voltage>
The charge injection property was evaluated under the same conditions as above, except that the potential difference between the charging blade and the charging roller was changed to −200V.
The injected charge and the injected charge distribution were evaluated from the change in charge amount ΔQ/M (unit: μC/g) and the change in charge amount distribution when the potential difference was 0 V and −200 V. In this evaluation, the larger the charge amount difference ΔQ/M (unit: μC/g) between the potential differences of 0 V and −200 V, the better the charge injection property even at a low voltage, indicating a high charge amount.
The evaluation results of Example 1 are shown in Table 5.
<Charge injection at low voltage>
A: ΔQ/M is greater than 20 μC/g B: ΔQ/M is greater than 10 μC/g and less than 20 μC/g C: ΔQ/M is greater than 5 μC/g and less than 10 μC/g D: ΔQ/M is less than 5 μC/g

<Examples 2 to 40 and Comparative Examples 1 to 6>
The evaluation was carried out in the same manner as in Example 1, except that the toner to be filled was changed as shown in Table 5. The evaluation results are shown in Table 5.

Claims (13)

A toner having toner particles containing a binder resin,
the toner particles contain a condensation product of an organosilicon compound,
In a time-of-flight secondary ion mass spectrometry (TOF-SIMS) of the toner particles,
the normalized intensity of a silicon ion (m/z 28) represented by the following formula (I) derived from a condensation product of the organosilicon compound is 7.00×10 ⁻⁴ or more and 3.00×10 ⁻² or less;
Normalized silicon ion intensity (m/z28)={ion intensity of silicon ion (m/z28)}
/ {total ion intensity at m / z 0.5 to 1850} ... (I)
the normalized intensity of silicon ions (m/z 28) measured by time-of-flight secondary ion mass spectrometry after sputtering the toner particles with an Ar gas cluster ion beam (Ar-GCIB) under the following condition (A) is 6.99×10 ⁻⁴ or less;
(A) Acceleration voltage: 5 kV, current: 6.5 nA, raster size: 600 x 600 μm, irradiation time: 5 sec/cycle, sputtering time: 250 sec
The toner has fine particles on the surface of the toner particles,
The toner is characterized in that the fine particles have at least one selected from the group consisting of polyvalent acid metal salt fine particles which are a reaction product of a compound containing at least one of Ti and Al elements with a polyvalent acid, strontium titanate fine particles, titanium oxide fine particles, and aluminum oxide fine particles. the normalized intensity of the silicon ion (m/z28) of the toner particles is 7.00×10 ⁻⁴ or more and 8.00×10 ⁻³ or less;
2. The toner according to claim 1, wherein after the toner particles are sputtered under the condition (A), the normalized intensity of the silicon ions (m/z 28) measured with a time-of-flight secondary ion mass spectrometer is 6.00×10 ⁻⁴ or less. The toner according to claim 1 or 2, wherein the fine particles are polyvalent acid metal salt fine particles that are a reaction product of a compound containing at least one of Ti and Al elements and a polyvalent acid. The toner according to claim 3, wherein the polyvalent acid of the polyvalent acid metal salt fine particles is phosphoric acid. The toner according to claim 3 or 4, wherein the metal element of the polyvalent acid metal salt fine particles is a Ti element. The toner according to any one of claims 1 to 5, wherein the total content of Ca and Mg elements in the toner particles is 23 μmol/g or less as measured by an inductively coupled plasma emission spectrometer. 7. The toner according to claim 1, wherein the condensation product of the organosilicon compound is a silane-modified resin R having a structure represented by the following formula (1):

(In the formula (1), P ¹ represents a polymer moiety, L ¹ represents a single bond or a divalent linking group, R ¹ to R ³ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 or more carbon atoms, an alkoxy group having 1 or more carbon atoms, an aryl group having 6 or more carbon atoms, or a hydroxy group; m
represents a positive integer, and when m is 2 or more, a plurality of L ^{1 s} , a plurality of R ^{1 s} , a plurality of R ^{2 s} , and a plurality of R ^{3 s} may be the same or different, provided that Si is bonded to at least one carbon, and at least one of R ¹ to R ^{3 s} is condensed with an organosilicon compound. 8. The toner according to claim 7, wherein at least one of R ¹ to R ³ represents an alkoxy group or a hydroxy group having one or more carbon atoms. 8. The toner according to claim 7, wherein the groups among R ¹ to R ³ which are not condensed with the organosilicon compound each independently represent an alkoxy group or a hydroxy group having one or more carbon atoms. The toner according to any one of claims 7 to 9, wherein ^P1 represents a styrene acrylic resin moiety or a polyester resin moiety. The toner according to any one of claims 7 to 10, wherein L ¹ is represented by the following formula (2):

( ^R5 in formula (2) represents a single bond, an alkylene group or an arylene group. (*) represents a bonding site to ^P1 in formula (1), and (**) represents a bonding site to the silicon atom in said formula (1).) The toner according to any one of claims 1 to 11, wherein the content of the fine particles is 0.10 parts by mass or more and 0.30 parts by mass or less per 100 parts by mass of the toner particles. The toner according to any one of claims 1 to 12, wherein the fine polyvalent acid metal salt particles have a number average particle diameter DA of 5 nm to 30 nm.